Results and Discussion

4.3 Nano CaSO4: PA Composites

4.3.1 Characterization of nano CaSO4: PA composites

The X-ray diffractograms of the nanocomposites are shown in fig 4.15 and 4.16.

The absence of peaks indicates that nano CaSO4 dispersed through out the

matrix; whereas commercial CaSO4 filled PA composite shows a peak at 19.82 o.

This might be due to micron size of filler. Presence of peaks indicates that filler

CaSO4 get agglomerated (17). For 10 nm CaSO4, there was no peak. While for

commercial CaSO4, peak was observed at 19.82 o. This shifting of peak at lower

angle shows less intercalation of polymer chains into the nano inorganic filler (16,

18, and 31).

Fig 4.15: XRD of different nanocomposites a) Commercial CaSO4 PA

Nanocomposite

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 84
 Results and Discussion

Fig 4.16: XRD of different nanocomposites a) PA 23 nm CaSO4

4.3.2 Thermal properties of nano CaSO4: PA composites

4.3.2.1 Thermo gravimetric analysis of nano CaSO4: PA composites

The weight loss curves, as functions of the temperature for nano CaSO4 (10, 15

and 23 nm) filled PA composites, are shown in fig 4.17. The thermal properties of

pure PA, commercial CaSO4, nano CaSO4 (23, 15 and 10 nm) are shown in figs

4.17 to 4.19. It can be observed that the incorporation of nano CaSO 4 in PA with

reduced particle size shows better thermal stability as compared to commercial

CaSO4 filled in PA. 2 wt % of nano CaSO4 (23, 15, and 10 nm) filled in PA shows

decomposition temperatures as 445.30, 445.45, and 457.23 0C respectively,

while for commercial CaSO4 decomposition temperature is 439.92 0C for same wt

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 85
 Results and Discussion

% of filler loading. Whereas, 12 wt % loading of filler, decomposition

temperatures are recorded as 449.00, 456.23, and 469.23 for nano CaSO 4 (23,

15 and 10 nm); while for commercial CaSO4, it is recorded as 442.23. This

enhancement in thermal stability is due to uniform dispersion of nano CaSO4

through out the matrix (19, 20).

Fig 4.17 TGA of 10 nm CaSO4 polyamide filled with various sizes of CaSO4.

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 86
 Results and Discussion

Fig 4.18 TGA of 15 nm CaSO4 polyamide filled with various sizes of CaSO4.

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 87
 Results and Discussion

Fig 4.19 TGA of 23 nm CaSO4 polyamide filled with various sizes of CaSO4.

4.3.2.2 Flammability of nano CaSO4: PA composites

The rates of flame retardency of different filler compositions are shown in fig

4.20. The nanosize CaSO4 filled in polyamide shows significant improvement in

flammability compared to that of commercial CaSO4 filled polyamide. The

flammability values are 3.65 and 2.54 sec/mm for 1 wt % of 10 nm size CaSO4

and commercial CaSO4 respectively. Whereas 4 wt % loading of 10 nm and

commercial CaSO4 shows flame retardency 4.98 and 3.01 sec/mm respectively.

It means, reduction in nanosize shows better improvement in flame retarding

properties. This might be due to the nano filler, which creates the effective char

layer on the surface (23), and it absorbs the heat of burning (endothermic). In

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 88
 Results and Discussion

addition, CaSO4 can delay the time before ignition and suppress the release of

smoke. CaSO4 with high activity can also absorb many substances (21,22),

including free radical and carbon. Besides that due shape of filler (needle like or

fiber like) creates the barrier through the bridging in between the two polymer

chains when the sample burns.

Commercial
5.5
23 nm

5 15nm
10nm
Rate of Burning [Sec/mm]

4.5

3.5

2.5

2
0 1 2 3 4 5
Wt % of Filler

Fig-4.20: Flame retardancy of PA filled with various sizes and varying wt %

of CaSO4

4.3.3 Physical properties of nano CaSO4- PA composites

4.3.3.1 Hardness of nano CaSO4: PA composites

Fig. 4.21 shows the effect of weight percentage of filler loading (nano and

Commercial CaSO4) on hardness of polyamide composites. It is observed that

hardness of nano CaSO4 filled polyamide nanocomposites was higher than that

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 89
 Results and Discussion

of commercial CaSO4 filled polyamide composites. Also the hardness of 10 nm

CaSO4 found to be more improved than that of 23 and 15 nm sizes of CaSO4.

The hardness is recorded as 87 and 77 for 1 wt % loading of 10 nm and

commercial CaSO4 respectively, while 4 wt % loadings of 10 nm and commercial

CaSO4 showed hardness 99 and 82 respectively. This might be due to uniform

dispersion of nano CaSO4, which makes the surface of the composite hard and

tough.

Commercial
105
23 nm
100 15nm
10nm
95
Hardness (Shore D)

90

85

80

75

70
0 1 2 3 4 5
Wt% of Filler

Fig-4.21: Hardness of PA filled with various sizes and varying wt %

of CaSO4

4.3.4 Mechanical properties of nano CaSO4: PA composites

4.3.4.1 Tensile strength of nano CaSO4: PA composites

A relation between weight percentage of filler loading (nano and Commercial

CaSO4) and tensile strength of polyamide composites is shown in fig 4.22. It is

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 90
 Results and Discussion

observed that tensile strength of nano CaSO4 filled polyamide nanocomposites

was higher than that of commercial CaSO4 filled polyamide composites. Also the

tensile strength of 10 nm CaSO4 was found to be more improved than that of 23

and 15 nm sizes of CaSO4. The tensile strength is recorded as 109 MPa and 96

MPa for 1 wt % loading of 10 nm and commercial CaSO4 respectively.

Whereas, 4 wt % loading of 10 nm and commercial CaSO4 shows tensile strength

135 MPa and 102 MPa respectively. It means nano filler provides higher tensile

strength compared to commercial CaSO4. This increment in tensile strength is

due to uniform dispersion of nano filler through out the matrix. Also due to

reduction in particles size of nano CaSO4 that forms smaller spherullits for

shorter period of time. Moreover, during processing, rate of transfer of heat is

uniform from particle to particle due to fine sizes of nano CaSO4, which leads in

formation of composite without any failure. This increment in tensile strength is

also due to the morphology and shape of the filler. CaSO 4 found to be fiber like or

needle like which might be act as a spacer or Bridger in between the two polymer

chains and align them in an order (figs 4.23,4.24). So the further development of

the crack minimizes. This increment was also due to higher nucleation and

orientation of polymer chains with and without filler (22,23,28). The uniform

dispersion of nano CaSO4 is evidenced from SEM images as shown in fig 4.25 to

4.27. During tensile test the fine cracks are developed on specimen shown in

SEM photograph (fig 4.23 to 4.27).

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 91
 Results and Discussion

Fig- 4.22: Tensile strength of PA filled with various sizes and varying wt %
of CaSO4.

Fig 4.23 SEM of micro crack of 1 wt % loading of 10 nm CaSO4 filled

Polyamide composite.

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 92
 Results and Discussion

Fig 4.24 SEM of micro crack of 4 wt % loading of 10 nm CaSO4 filled

Polyamide composite

Fig 4.25 SEM of micro crack of 1 wt % loading of commercial CaSO4 filled

Polyamide composite

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 93
 Results and Discussion

Fig 4.26 SEM of micro crack of 4 wt % loading of commercial CaSO4 filled

Polyamide composite.

Fig 4.27 SEM micrograph of 4-wt % of commercial CaSO4 polyamide

Composite

4.3.4.2 Elongation at break of nano CaSO4: PA composites

Fig 4.28 shows elongation at break of polyamide nanocomposites with varying wt

% of loading. It was found that with increase in weight percentage of filler

loading, elongation at break decreased. There was continuous decrement in

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 94
 Results and Discussion

elongation at break with increase in amount of filler loading for all compositions.

10 nm CaSO4 filled polyamide composite showed more decrement in elongation

at break compared to other two sizes of CaSO4. This might be due to hard nature

of polyamide as well as nano inorganic filler. 1 % loading of nano CaSO4 shows

elongation at break 20.14, 19.32, 16.54 and 14.54 % for commercial, 23,15 and

10 nm CaSO4 respectively. Whereas, 4 wt % loadings of commercial, 23,15, and

10 nm CaSO4 show elongation at break 14.67,16, 9.76 and 8.96 % respectively.

Addition of filler decreases the elongation at break of composites. This is due to

the increment in spherullits formation with reduction in size and increase in

percentage of filler (27). Moreover it provides catastrophic failure to the

specimen with crack propagation, and thus decreases the extensibility of the

composite. The structure of filler is one region behind decrement in elongation at

break which provides less shearing to the polymer chains with increase in

amount of filler loading. This crack development is evidenced from SEM

photograph (fig 4.23 to 4.27).

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 95
 Results and Discussion

Commerc ial
45
23 nm
40
15nm
35
10nm
30
Elongation @ Break

25
20
15
10
5
0
0 1 2 3 4 5
Wt% o f Fille r

Fig-4.28: Elongation at break of PA filled with various sizes and varying

wt %of CaSO4

4.3.4.3 Young’s modulus of nano CaSO4: PA composites

A relation between weight percentage of filler loading (nano and Commercial

CaSO4) and Young’s modulus of polyamide composites is shown in fig 4.29. It is

observed that Young’s modulus of nano CaSO4 filled polyamide nanocomposites

was higher than that of commercial CaSO4 filled polyamide composites. Also, the

Young’s modulus of 10 nm CaSO4 was found to be more than that of 23 and 15

nm sizes of CaSO4. 1 wt % loading of, 10 nm CaSO4 shows Young’s modulus

3802 MPa, while same wt % of loading of commercial CaSO4 shows Young’s

modulus 3650 MPa. Whereas, 4 wt % loadings of 10 nm CaSO4 and commercial

CaSO4 shows Young’s modulus 4002 MPa and 3725 MPa.

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 Results and Discussion

Fig-4.29: Young’s Modulus of PA filled with various sizes and varying wt %

of CaSO4.

Increment is more appreciable for nano CaSO4 as compared to commercial

CaSO4. (17) It can be summarized from the results that the reduced nano size of

CaSO4 provides better thermal, physical and mechanical properties than the

commercial CaSO4 to the PA composites. As the nano particles are so small that

they disperse uniformly in the matrix and intercalate polymer chains to provide

them an order, therefore surface area of polymer chains increases. However, a

higher amount of nano CaSO4 may get agglomerated and therefore the behavior

of agglomerated part of nano CaSO4 may be assumed as commercial CaSO4,

which is less dispersed in comparison to nano CaSO4 in the matrix.

Ph.D Thesis, Mr. Shriram S. Sonawane, UDCT, North Maharashtra University, Jalgaon Page 97